Mineral oil composition



Fatented Jan. if, 1949.

orr cs MINERAL DECOMPOSITION Edward A. obemgm, Woodbury, N. J.,. assignor to Sooony-Vacuum Oil Company, Incorporated,

a corporation of New York No Drawing. Application at s, 1945,

Serial No. 603,586

6 Claims. (Cl. 252s1.5

This invention has to do in a general way with mineral oil compositions and is more particularly related to compositions comprised of mineral oil and a minor proportion of an added ingredient which will improve the oil in one or more important r cts.

It is well known to those familiar with the art that mineral oil fractions refined for their various uses are in and of themselves usually deficient in one or more respects so that their practical utility is limited even in the particular field for which they have been refined. For example, mineral oil fractions refined for use as lubricants have a tendency to oxidize under conditions of use, with the formation of sludge or acidi: oxidation products; also, the lighter fractions such as gasoline and kerosene tend to oxidize with the formation of color bodies, gum, etc. In order to prevent the formation of these products and thereby extend the useful life of the oil fraction, it 'is common practice to blend with such oil fraction an additive ingredient which will inhibit oxidation, such ingredients being known to the trade as oxidation inhibitors, antioxidants, sludge inhibitors, gum inhibitors, etc.

It is also the practice to add other ingredients to mineral oil fractions for the purpose of improving olliness characteristics and the wear-reducing action of such mineral oils when they are used as lubricants, particularly when the oils are used for the purpose of lubricating metal surfaces which are engaged under extremely high pressures and at high rubbing speeds.

Various other ingredients have been developed for the purpose of depressing the pour point of mineral oil fractions which have been refined for use as lubricants. Most refining treatments provide oils containing a small amount of wax which, without the added ingredient, would tend to crystallize at temperatures which render the oil impracticable for use under low temperature conditions. Additive agents have also been developed for improving the viscosity index of lubricating oil fractions. In the case of internal combustion engines, particularly those operating with high cylinder pressures, there is a decided tendency for the ordinary lubricating oil fractions to form carbonaceous deposits which cause the piston rings to become stuck in their slots and which 1111 the slots in the oil ring or rings, thus materially reducing the efficiency of the engine. Ingredients have been developed which, when added to the oil, will reduce this natural tendency of the oil to form deposits-which interfere with the function of the piston rings.

It has also been discovered that certain types of recently-developed hard metal alloys, such as cadmium-silver alloy bearings, are attacked by ingredients in certain types of oils, particularly oils of high viscosity index obtained by various methods ofsolvent-refining. This corrosive action on such alloys has led to the development of corrosion-inhibitors which may be used in soivent-reflned oils to protect such bearing metals against this corrosive action. 7

In the lighter mineral oil fractions, such as those used for fuel purposes, particularly in internal combustion engines, it has been found that the combustion characterstics of the fuel may be controlled and improved by adding minor proportions of various improving ,agents thereto.

The various ingredients which have been developed for use in mineral oil fractions to improve such fractions in the several characteristics enumerated above are largely specific to their particular applications. Therefore, it has been the practise to add a separate ingredient for each of the improvements which is to be effected.

The present invention is predicated upon the discovery of a group or class of oil-soluble condensation products or compounds which, when gen compound selected from the group consisting of ammonia and an amide. The condensation products may be represented by the following general formula:

l -Ri U\ /NRz H R;

wherein R1 and R: are hydrogen, alkyl, aralkyl, aryl, alkaryl or cycloalkyl and may be the same or different groups; and R2 is either hydrogen or a group wherein R4 is alkyl, aralkyl, aryl, alkaryl or cycloalkyl.

Aldehydes contemplated by the present invention are the aliphatic aldehydes, typified by formaldehyde (such as trioxymethyiene), acetaldehyde, etc.; aromatic aldehydes representative of which is benzaldehyde; heterocyclic aldehydes, such as furfural; etc. The aldehyde may contain a substituent group such as hydroxyl, halogen, nitro and the like; in short, any substituent which does not take a major part in the reaction. Preference, however, is given to the aromatic aldehydes, benzaldehyde being particularly preferred.

The heterocyclic hydroxyaromatic compounds contemplated herein are those represented by the general formula II: 7

wherein the 7 carbon atom is joined to a hydrogen atom. Analogs of these compounds in which one radical of the amide. Of the amides, acetamide is preferred, although ammonia is particularly preferred herein.

Methods for the preparation of these condensation products are well known in the art; for example, they are described in Chemical Abstracts, vol. 31, page 3921 (1937) and vol. 32, page 1701 (1938). Accordingly, it is believed unnecessary to describe at length the reaction conditions involved in the preparation of these condensation products, one example being provided below by way of illustration.

EXAM? (a) Reactants.80 grams of benzaldehyde, 20 grams of 8-hydroxyquinoline, ammonia gas, 140 cc. absolute ethyl alcohol (solvent).

(b) Procedure.-Fifteen grams of benzalde hyde were added to 70 cos. of absolute ethyl alcohol and the resulting mixture was saturatedwith ammonia gas. The remainder of the benzaldehyde and the 8-mrdroxyquinoline were dissolved in '70 cos. of absolute ethyl alcohol. The two solutions thus obtained were mixed and were refluxed at 80 C. for one hour. After standing overnight, the reaction mixture was saturated with ammonia gas whereupon a white crystalline precipitate was formed. The crystalline precipitate was separated from the reaction mixture by filtration, was washed with absolute ethyl alcohol and dried. The product had a melting point of 140-1 C. (uncorrected) and contained 8.2 per cent nitrogen (theoretical, 8.3 per cent). The product-Product One-is therefore 7, 8, 6'- quinoline- (1',3'-diphenyl) -4',2' oxazine.

As stated hereinabove, the condensation products contemplated herein and illustrated by the above example, when added to hydrocarbon fractions in minor amounts, have been found to improve the same in several important respects. This phenomenon is demonstrated in the following tables, which contain the results of the various tests conducted to determine the effectiveness of these condensation products as addition agents for hydrocarbon fractions.

Ann-0mm m Gasotml.

A sweetened thermally-cracked gasoline having a boiling range of to 400 F. was subjected to the oxygen bomb test. A 100 cc. sample of gasoline, in an 8 ounce, open glass bottle, is placed in a stainless steel bomb under 100 pounds pressure of oxygen. The bomb is placed in a boiling water bath. The bomb is kept in the bath until the pressure begins to decrease. The introduction is taken as the time interval measured from the time the bomb is placed in the bath until the pressure starts to decrease. The gasoline had an induction period of minutes. However, when the same gasoline had incorporated therein 0.1 per cent of Product One, the induction period was 180 minutes.

Soconr-Vacmm Timsnns Tzsr Twenty-five cc. samples of a furfural-reflned Rodessa crude of Saybolt Universal viscosity of 150 seconds at 100 F. and of a blend of this same oil and Product One were subjected to the following test to determine the efiectiveness of the condensation products contemplated by this invention as inhibitors for turbine oils: To each sample were added 1 gram of iron granules and 24 inches of 18 gauge copper wire. The samples were then heated to a temperature of 200 F. with 5 liters of air per hour bubbling therethrough. Two cos. of distilled water were added each day. The results of the tests which were made for color and acidity or neutralization number and amount of sludge formed after certain time intervals are set forth in Table 1 below.

Table 1 Per Cent Lovibond Sludge Addition Agent Added Hours C N. N. in mgms N e 162 245 17.8 389 Product One 0.1 161 1.5 0.01 15 D0 552 27 12. 6 34 Coasosrou Trs'r In the test the condensation product was blended with a Pennsylvania solvent-refined oil of Saybolt Universal viscosity of 53 seconds at 210 F., and a section of a bearing having a cadmiumsilver alloy surface and weighing about 6 grams was added to this blend. The oil was heated to C. for 22 hours while a stream of air was bubbled against the surface of the bearing. The loss in weight of the bearing during this treatment measures the amount of corrosion that has taken place. A sample of the uninhibited oil was subjected to the same test at the same time, and the difference between the losses in weight of the two bearing sections demonstrated conclusively the eflectiveness of the condensation products Ormnon Test To demonstrate the effectiveness of these condensation products under actual operating conditions of an automotive engine, an unblended oil and a blend of the same 011 and Product One were subjected to the Lauson engine test. The tests were carried out in a single-cylinder Lauson engine operated continuously over a time interval of 16 hours with the cooling medium held at a temperature of about 212 F. and the oil temperature held at about 280 F. The engine was operated at a speed of about 1830 R. P. M. At the end of each test the oil was tested for acidity (N. N.) and viscosity. The results of these tests are shown in Table III below, wherein the unblended oil is a solvent refined oil of Saybolt Universal viscosity of 45 seconds at 210 F.

The amount of improving agent used varies with the hydrocarbon fraction or lubricating oil fraction with which it is blended and with the properties desired in the final oil composition. These condensation products may be added to hydrocarbon fractions in amounts of from about 0.001 per cent to about per cent, but amounts of from about 0.01 per cent to about 2 per cent are preferred for the purposes of this invention.

It is to be understood that although I have described certain preferred procedures which may be followed in the preparation of the novel condensation products contemplated herein as improving agents for hydrocarbon fractions .and have indicated representative reactants for use in their preparation, such procedures and reactants are merely illustrative and this invention is not to be considered as limited thereto or thereby but includes within its scope such changes and modifications as fairly come within the language of the appended claims.

I claim:

1. An improved normally liquid hydrocarbon fraction selected from the group consisting of a normally liquid hydrocarbon fraction adapted for use as a fuel and a normally liquid hydrocarbon fraction adapted for use as a lubricant, said improved hydrocarbon fraction containing a minor proportion of a condensation product having the general formula:

wherein R1 and R3 are aryl radicals.

2. .An improved normally liquid hydrocarbon fraction selected from the group consisting of a normally liquid hydrocarbon fraction adapted for use as a fuel and a normally liquid hydrocarbon iraction adapted for use as a lubricant, said improved hydrocarbon fraction containing a minor proportion, from about 0.001 per cent to about 5 per cent, of a condensation product having the general formula;

wherein R1 and R3 are aryl radicals.

3. A gasoline fuel containing a minor proportion of a condensation product having the general formula:

wherein R1 and R3 are aryl radicals.

6. An improved normally liquid hydrocarbon fraction adapted for use as a lubricant containing a minor proportion of 7,8,5,6-quinoline-(1',3- diphenyl) -4,2' oxazine.

EDWARD A. OBERRIGHT.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Name Date Bartram Nov. 24, 1936 Number Certificate of Correction Patent No. 2,458,526. January 11, 1949.

' EDWARD A. OBERRIGHT It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows:

eriogolunm 4, line 9, strike out the word "introduction and insert instead induction find that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Ofiice.

Signed and sealed this 31st day of May, A. D. 1 949.

THOMAS F. MURPHY,

Assistant Commissioner of Patents. I 

